Process for the antimicrobial treatment of fiber materials

1. A process for durable antimicrobial treatment of natural or synthetic polyamide or cellulosic fibers, comprising

reacting an inclusion complex of a fiber-reactive cyclodextrin containing an antimicrobial agent with said fibers, and having fiber reactive groups bonded to the cyclodextrim wherein the antimicrobial agent is selected from the group consisting of

(a) halogeno-o-hydroxydiphenyl compounds of the formula

 wherein

X is oxygen, sulfur or —CH 2 —,

Y is chloro or bromo,

Z is SO 2 H, NO 2 or C 1 –C 4 -Alkyl,

r is 0 to 3,

o is 0 to 3,

p is 0 or 1,

m is 0 or 1 and

n is 0 or 1;

and at least one of r or o is ≠0,

and non-halogenated hydroxydiphenyl ether compounds of the formula

 wherein

U 1 and U 2 are independently of each other hydrogen, hydroxy, unsubstituted or hydroxy-substituted C 1 –C 20 alkyl, C 5 –C 7 cycloalkyl, C 1 –C 6 alkylcarbonyl, C 1 –C 20 alkoxy, phenyl or phenyl-C 1 –C 3 -alkyl;

U 3 is hydrogen, C 1 –C 20 alkyl, C 1 –C 20 alkoxy or C 1 –C 6 alkylcarbonyl; and

U 4 is hydrogen, unsubstituted or hydroxy-substituted C 1 –C 20 alkyl, C 5 –C 7 cycloalkyl, hydroxy, formyl, acetonyl, C 1 –C 6 alkylcarbonyl, C 2 –C 20 alkenyl, carboxy, carboxyC 1 –C 3 alkyl, C 1 –C 3 alkylcarbonyl-C 1 –C 3 alkyl or carboxyallyl.

2. A process according to claim 1 , wherein the antimicrobial agent (a) is a compound of formula (1), wherein

X is oxygen, sulfur or —CH 2 —, and

Y is chloro or bromo,

m is 0,

n is 0 or 1,

o is 1 or 2,

r is 1 or 2 and

p is 0.

3. A process according to claim 1 , wherein the antimicrobial agent (a) is a compound of formula

wherein

X is —O— or —CH 2 —;

m is 1 to 3; and

n is 1 or 2.

4. A process according to claim 1 wherein the antimicrobial agent (a) is a compound of formula

5. A process according to claim 1 wherein the antimicrobial agent (a) compound of formula

6. A process according to claim 1 wherein U 1 and U 3 are C 1 –C 4 alkyl and U 2 and U 4 are hydrogen.

7. A process according to claim 1 , wherein the fiber-reactive group of the cyclodextrin is a nitrogen-containing heterocycle having at least one substituent selected from the group consisting of halogen and pyridinium radicals.

8. A process according to claim 1 , wherein the fiber-reactive group of the cyclodextrin is

a) a triazine group of formula

 wherein

R 10 is fluorine, chlorine or unsubstituted or carboxy-substituted pyridinium, and

R 11 is as defined above for R 10 or is a radical of formula —OR 12 or —N(R 13 )R 14 , wherein

R 12 is hydrogen, alkali, C 1 –C 8 alkyl which is unsubstituted or substituted by hydroxy or C 1 –C 4 alkoxy, and

R 13 and R 14 , independently from each other, are hydrogen; C 1 –C 8 alkyl which is unsubstituted or substituted by C 1 –C 4 alkoxy, hydroxy, sulfo, sulfato or carboxy; or phenyl which is unsubstituted or substituted by C 1 –C 4 alkyl, C 1 –C 4 alkoxy, halogen, nitro, carboxy or sulfo;

b) or is a pyrimidinyl group of formula

 wherein

one of radicals R 15 and R 16 is fluorine or chlorine and the other one of radicals R 15 and R 16 is fluorine, chlorine, or is a radical of formula —OR 12 or —N(R 13 )R 14 as defined above, and

R 17 is C 1 –C 4 alkylsulfonyl, C 1 –C 4 alkoxysulfonyl, C 1 –C 4 alkoxycarbonyl, C 2 –C 4 alkanoyl, chlorine, nitro, cyano, carboxyl or hydroxyl;

c) or is a dichloroquinoxaline group of formula

9. A process according to claim 8 , wherein the fiber-reactive group of the cyclodextrin is

a triazine group of formula

 wherein

R 10 is chlorine, and

R 11 is a radical of formula —OR 12 , wherein R 12 is hydrogen, an alkali metal or C 1 –C 8 alkyl.

10. A process according to claim 1 , wherein the cyclodextrin contains 2 to 3 fiber-reactive groups.

11. A process according to claim 1 , wherein the application of the inclusion complex is carried out in an aqueous medium containing 2 to 100 g per liter of the inclusion complex.

12. A process according to claim 1 , wherein the application of the inclusion complex is carried out at a pH of from 4 to 7.

13. A process according to claim 1 , wherein the application of the inclusion complex is carried out by a padding technique.

14. A process according to claim 1 , wherein the fiber material, after application of the inclusion complex, is treated at a temperature of 100 to 200° C.

15. An aqueous composition comprising an inclusion complex of a fiber-reactive cyclodextrin having fiber reactive groups bonded to the cyclodextrin and containing an antimicrobial agent, which agent is selected from the group consisting of

(a) halogeno-o-hydroxydiphenyl compounds of the formula

 wherein

X is oxygen, sulfur or —CH 2 —,

Y is chloro or bromo,

Z is SO 2 H, NO 2 or C 1 –C 4 -Alkyl,

r is 0 to 3,

o is 0 to 3,

p is 0 or 1,

m is 0 r 1 and

n is 0 or 1;

and at least one of r or o is ≠0,

and non-halogenated hydroxydiphenyl ether compounds of the formula

 wherein

U 1 and U 2 are independently of each other hydrogen, hydroxy, unsubstituted or hydroxy-substituted C 1 –C 20 alkyl, C 5 –C 7 cycloalkyl, C 1 –C 8 alkylcarbonyl, C 1 –C 20 alkoxy, phenyl or phenyl-C 1 –C 3 -alkyl;

U 3 is hydrogen, C 1 –C 20 alkyl, C 1 –C 20 alkoxy or C 1 –C 6 alkylcarbonyl; and

U 4 is hydrogen, unsubstituted or hydroxy-substituted C 1 –C 20 alkyl, C 5 –C 7 cycloalkyl, hydroxy, formyl, acetonyl, C 1 –C 6 alkylcarbonyl, C 2 –C 20 alkenyl, carboxy, carboxyC 1 –C 3 alkyl, C 1 –C 3 alkylcarbonyl-C 1 –C 3 alkyl or carboxyallyl.

16. An inclusion complex of a fiber-reactive cyclodextrin having fiber reactive group bonded to the cyclodextrin and containing an antimicrobial agent, which agent is selected from the group consisting of

(a) halogeno-o-hydroxydiphenyl compounds of the formula

 wherein

X is oxygen, sulfur or —CH 2 —,

Y is chloro or bromo,

Z is SO 2 H, NO 2 or C 1 –C 4 -Alkyl,

r is 0 to 3,

o is 0 to 3,

p is 0 or 1,

m is 0 or 1 and

n is 0 or 1;

and at least one of r or o is ≠0,

and non-halogenated hydroxydiphenyl ether compounds of the formula

 wherein

U 1 and U 2 are independently of each other hydrogen, hydroxy, unsubstituted or hydroxy-substituted C 1 –C 20 alkyl, C 5 –C 7 cycloalkyl, C 1 –C 8 alkylcarbonyl, C 1 –C 20 alkoxy, phenyl or phenyl-C 1 –C 3 -alkyl;

U 3 is hydrogen, C 1 –C 20 alkyl, C 1 –C 20 alkoxy or C 1 –C 8 alkylcarbonyl; and

U 4 is hydrogen, unsubstituted or hydroxy-substituted C 1 –C 20 alkyl, C 5 –C 7 cycloalkyl, hydroxy, formyl, acetonyl, C 1 –C 8 alkylcarbonyl, C 2 –C 20 alkenyl, carboxy, carboxyC 1 –C 3 alkyl, C 1 –C 3 alkylcarbonyl-C 1 –C 3 alkyl or carboxyallyl.

17. A process for the preparation of a fiber-reactive inclusion complex as defined in claim 16 , which comprises forming an inclusion complex of a fiber-reactive cyclodextrin with at least one antimicrobial agent as defined in claim 16 at a pH of ≧9.

18. A process for the preparation of a fiber-reactive inclusion complex as defined in claim 16 , which comprises the steps of

a) forming an inclusion complex of a cyclodextrin which contains at least one antimicrobial agent as defined in claim 16 ; and then

b) introducing at least one fiber-reactive group into the cyclodextrin in the inclusion complex obtained according to step a).

19. A process according to claim 18 wherein the inclusion complex obtained according to step a) is processed directly without intermediate drying.

20. A process according to claim 1 , wherein the cellulosic fiber is cotton.

21. A process according to claim 1 , wherein the fibers are in the form of a woven or knitted fabric, a nonwoven textile, a carpet, yam or staple fiber.